JP2009285882A - Photocatalyst coated body and photocatalyst coating liquid therefor - Google Patents
Photocatalyst coated body and photocatalyst coating liquid therefor Download PDFInfo
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- JP2009285882A JP2009285882A JP2008138186A JP2008138186A JP2009285882A JP 2009285882 A JP2009285882 A JP 2009285882A JP 2008138186 A JP2008138186 A JP 2008138186A JP 2008138186 A JP2008138186 A JP 2008138186A JP 2009285882 A JP2009285882 A JP 2009285882A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 236
- 238000000576 coating method Methods 0.000 title claims abstract description 126
- 239000011248 coating agent Substances 0.000 title claims abstract description 122
- 239000007788 liquid Substances 0.000 title claims abstract description 52
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- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 52
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- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 31
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- 229940121375 antifungal agent Drugs 0.000 claims description 23
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 9
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
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- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
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- 241000972756 Boronia Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
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- 229910002367 SrTiO Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
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- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
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- 229910052791 calcium Inorganic materials 0.000 description 1
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- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
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Images
Abstract
Description
本発明は防汚性、有害物質分解性、耐光性およびカビや藻の繁殖抑制などに優れた効果を発現する光触媒塗装体に関する。 The present invention relates to a photocatalyst-coated body that exhibits excellent effects such as antifouling property, decomposability of harmful substances, light resistance, and inhibition of mold and algae growth.
酸化チタンなどの光触媒が、近年建築物の外装材など多くの用途に利用されている。基材表面に光触媒を塗装することにより、光エネルギーを利用してセルフクリーニング機能、ＮＯｘ、ＳＯｘ等有害物質の分解機能、カビや藻などの繁殖を抑制する機能を付与することが可能となる。このような光触媒塗装体を得る場合、ベースとなる基材と光触媒の間に、接着および／または光触媒による基材表面の劣化抑制を目的とした中間層を設けることが行われる。この中間層には、光触媒によるカビや藻の繁殖を抑制する機能を補完するため、特に日陰など光触媒機能が発現しにくい部位においても、カビや藻の繁殖を抑制する性能を確保する目的で、有機防カビ剤を添加する例が見られる。このような光触媒を塗装した光触媒塗装体を得る技術としては、以下のものが知られている。 In recent years, photocatalysts such as titanium oxide have been used in many applications such as exterior materials for buildings. By coating a photocatalyst on the surface of the substrate, it is possible to provide a self-cleaning function, a function of decomposing harmful substances such as NOx and SOx, and a function of suppressing the growth of fungi and algae using light energy. When obtaining such a photocatalyst-coated body, an intermediate layer is provided between the base material serving as the base and the photocatalyst for the purpose of adhesion and / or suppression of deterioration of the base material surface due to the photocatalyst. In this intermediate layer, in order to supplement the function to suppress the growth of mold and algae by photocatalyst, in order to ensure the ability to suppress the growth of mold and algae, especially in areas where the photocatalytic function is difficult to express, such as shade, An example of adding an organic fungicide can be seen. The following are known as techniques for obtaining a photocatalyst-coated body coated with such a photocatalyst.
ベースとなる基材と光触媒の間に、接着および／または光触媒による基材表面の劣化抑制を目的としたシリコーン変性樹脂などの中間層を設ける技術が知られている。（例えば、特許文献１（国際公開第９７／００１３４号パンフレット）参照）。 A technique is known in which an intermediate layer such as a silicone-modified resin is provided between a base material serving as a base and a photocatalyst for the purpose of adhesion and / or suppression of deterioration of the base material surface by the photocatalyst. (For example, refer to Patent Document 1 (International Publication No. 97/00134 pamphlet)).
またこのような中間層に、光触媒のカビや藻の繁殖を抑制する機能を補完するため、有機防カビ剤を添加する技術が知られている（特許文献２（特開２００１−２３２２１５号公報）参照））。 In addition, a technique for adding an organic antifungal agent to such an intermediate layer in order to complement the function of suppressing the growth of mold and algae of the photocatalyst is known (Patent Document 2 (Japanese Patent Laid-Open No. 2001-232215)). reference)).
また当該塗装体の耐久性を高める目的で、光触媒層に加水分解性シリコーン等のバインダー成分を添加する技術が知られている。（特許文献３（特開２０００−２１２５１０号公報）参照），（特許文献４（特開２００２−１３７３２２号公報）参照）。 A technique for adding a binder component such as hydrolyzable silicone to the photocatalyst layer is known for the purpose of enhancing the durability of the coated body. (See Patent Document 3 (Japanese Patent Laid-Open No. 2000-212510)), (See Patent Document 4 (Japanese Patent Laid-Open No. 2002-137322)).
光触媒層にバインダー成分として加水分解性シリコーンを添加した場合、加水分解性シリコーンが緻密な膜を形成するため、光触媒層を構成する粒子間の空隙を塞ぐ。その結果、中間層に添加した防カビ剤の溶出速度が小さくなり、防藻、防カビ機能を補完する目的が果たせなくなる不具合が発生する懸念がある。さらには加水分解性シリコーンの添加量によっては、光触媒層を透過するガスの拡散速度が小さくなり、光触媒による有害ガス分解機能が低下するなど、光触媒が本来有する機能をも喪失する懸念がある。 When hydrolyzable silicone is added as a binder component to the photocatalyst layer, the hydrolyzable silicone forms a dense film, so that the voids between the particles constituting the photocatalyst layer are blocked. As a result, the elution rate of the fungicide added to the intermediate layer is reduced, and there is a concern that a problem that the purpose of supplementing the anti-algae and fungicide functions cannot be achieved. Furthermore, depending on the amount of hydrolyzable silicone added, there is a concern that the function inherent to the photocatalyst may be lost, for example, the diffusion rate of the gas that permeates the photocatalyst layer decreases and the harmful gas decomposition function of the photocatalyst decreases.
また、充分な光触媒活性を得るために、光触媒層に含まれる光触媒を増量することが従来より行われているが、そのような塗膜構成にした場合、中間層が光触媒によって劣化する恐れがあり、さらには、中間層に含まれる有機防カビ剤が分解され、光触媒による防藻、防カビ機能を補完する目的が果たせなくなることなどの不具合を発生する懸念があった。また、光触媒を減量させると光触媒層での紫外線遮蔽効果が弱まり、塗膜および下地の紫外線劣化が懸念される。 In order to obtain sufficient photocatalytic activity, the amount of photocatalyst contained in the photocatalyst layer has been conventionally increased. However, in such a coating film structure, the intermediate layer may be deteriorated by the photocatalyst. In addition, there is a concern that the organic antifungal agent contained in the intermediate layer is decomposed, causing problems such as the algae prevention by the photocatalyst and the purpose of complementing the antifungal function cannot be achieved. Further, when the amount of the photocatalyst is reduced, the ultraviolet shielding effect in the photocatalyst layer is weakened, and there is a concern that the coating film and the underlying layer are deteriorated by ultraviolet light.
したがって、本発明は、防藻性、防カビ性、有害ガス分解性、親水性など光触媒本来の機能と、塗膜の耐候性、耐光性および塗膜の強度を両立させるとともに、防藻、防カビ性能を補完する有機防カビ剤の溶出も妨げない、光触媒を有する複合材およびそのための光触媒コーティング液を提供することを目的とする。 Therefore, the present invention achieves both the original functions of the photocatalyst such as antialgae, antifungal, harmful gas decomposability, hydrophilicity and the weather resistance, light resistance, and strength of the coating film, as well as antialgae, It is an object of the present invention to provide a composite material having a photocatalyst and a photocatalyst coating liquid therefor, which do not hinder the elution of an organic antifungal agent that complements the mold performance.
すなわち、本発明による光触媒塗装体は、基材と、該基材上に設けられる中間層と、該中間層上に設けられる光触媒層とを備えた光触媒塗装体であって、
前記中間層は有機防カビ剤および紫外線吸収剤を含んでなり、
前記光触媒層が、
１質量部以上２０質量部未満の光触媒粒子と、
７０質量部を超え９９質量部以下の無機酸化物粒子と、
０質量部以上１０質量部未満の加水分解性シリコーンとを、
前記光触媒粒子、前記無機酸化物粒子、および前記加水分解性シリコーンの合計量が１００質量部となるように含んでなるものである。
That is, the photocatalyst-coated body according to the present invention is a photocatalyst-coated body comprising a base material, an intermediate layer provided on the base material, and a photocatalyst layer provided on the intermediate layer,
The intermediate layer comprises an organic antifungal agent and an ultraviolet absorber,
The photocatalytic layer is
1 to 20 parts by mass of photocatalyst particles,
Inorganic oxide particles exceeding 70 parts by mass and 99 parts by mass or less;
0 part by mass or more and less than 10 parts by mass hydrolyzable silicone,
The total amount of the photocatalyst particles, the inorganic oxide particles, and the hydrolyzable silicone is 100 parts by mass.
また、本発明による光触媒コーティング液は、上記光触媒塗装体の製造に用いられる光触媒コーティング液であって、溶媒中に、
１質量部以上２０質量部未満の光触媒粒子と、
７０質量部を超え９９質量部以下の無機酸化物粒子と、
０質量部以上１０質量部未満の加水分解性シリコーンとを、
前記光触媒粒子、前記無機酸化物粒子、および前記加水分解性シリコーンの合計量が１００質量部となるように含んでなるものである。
Moreover, the photocatalyst coating liquid according to the present invention is a photocatalyst coating liquid used in the production of the photocatalyst-coated body.
1 to 20 parts by mass of photocatalyst particles,
Inorganic oxide particles exceeding 70 parts by mass and 99 parts by mass or less;
0 part by mass or more and less than 10 parts by mass hydrolyzable silicone,
The total amount of the photocatalyst particles, the inorganic oxide particles, and the hydrolyzable silicone is 100 parts by mass.
光触媒塗装体
本発明による光触媒塗装体は、基材上に設けられた、中間層上に設けられる光触媒層とを備えてなる。光触媒層は、１質量部以上２０質量部未満の光触媒粒子と、７０質量部を超え９９質量部以下の無機酸化物粒子と、任意成分としての０質量部以上１０質量部未満の加水分解性シリコーンとを含んでなる。
Photocatalyst coating body The photocatalyst coating body by this invention is provided with the photocatalyst layer provided on the intermediate | middle layer provided on the base material. The photocatalyst layer comprises 1 part by mass or more and less than 20 parts by mass of photocatalyst particles, more than 70 parts by mass and 99 parts by mass or less of inorganic oxide particles, and 0 to 10 parts by mass of hydrolyzable silicone as an optional component. And comprising.
すなわち、本発明による光触媒層は、光触媒粒子の配合割合が無機酸化物粒子よりも少ないことで、光触媒粒子の中間層との直接的な接触を最小限に抑えることができ、それにより中間層を浸食しにくくなるものと考えられる。 That is, in the photocatalyst layer according to the present invention, since the mixing ratio of the photocatalyst particles is smaller than that of the inorganic oxide particles, it is possible to minimize direct contact of the photocatalyst particles with the intermediate layer, thereby reducing the intermediate layer. It is thought that it becomes difficult to erode.
同時に、この構成により、有害ガス分解性、および所望の各種被膜特性（透明性、塗膜強度等）に優れた光触媒塗装体を得ることが可能となる。これらの幾つもの優れた効果が同時に実現される理由は定かではないが、以下のようなものではないかと考えられる。ただし、以下の説明はあくまで仮説にすぎず、本発明は何ら以下の仮説によって限定されるものではない。まず、光触媒層は、光触媒粒子および無機酸化物粒子の二種類の粒子から基本的に構成されるため、粒子間の隙間が豊富に存在する。光触媒層のバインダーとして広く用いられる加水分解性シリコーンを多量に使用した場合にはそのような粒子間の隙間を緻密に埋めてしまうため、ガスの拡散を妨げるものと考えられる。しかし、本発明の光触媒層は加水分解性シリコーンを含まないか、含むとしても光触媒粒子、無機酸化物粒子、および加水分解性シリコーンの合計量１００質量部に対して１０質量部未満としているため、粒子間の隙間を十分に確保することができ、そのような隙間によってＮＯｘやＳＯｘ等の有害ガスが光触媒層中に拡散しやすい構造が実現され、その結果、有害ガスが光触媒粒子と効率良く接触して光触媒活性により分解されるのではないかと考えられる。さらに光触媒粒子を非常に少なくしても、無機酸化物粒子と共存させることで、実用上十分な光触媒活性と塗膜強度、耐候性とが両立できることを見出した。 At the same time, this configuration makes it possible to obtain a photocatalyst-coated body excellent in harmful gas decomposability and various desired coating properties (transparency, coating strength, etc.). The reason why these excellent effects are realized at the same time is not clear, but is thought to be as follows. However, the following description is merely a hypothesis, and the present invention is not limited by the following hypothesis. First, since the photocatalyst layer is basically composed of two types of particles, photocatalyst particles and inorganic oxide particles, there are abundant gaps between the particles. When a large amount of hydrolyzable silicone widely used as a binder for the photocatalyst layer is used, it is considered that the gap between the particles is densely filled, and thus gas diffusion is hindered. However, the photocatalyst layer of the present invention does not contain hydrolyzable silicone or even if it contains less than 10 parts by mass with respect to 100 parts by mass of the total amount of photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone, Sufficient gaps between the particles can be secured, and a structure in which noxious gases such as NOx and SOx can easily diffuse into the photocatalyst layer is realized by such gaps. As a result, the noxious gas efficiently contacts the photocatalyst particles. Therefore, it is thought that it is decomposed by the photocatalytic activity. Furthermore, it has been found that even if the amount of photocatalyst particles is very small, by coexisting with inorganic oxide particles, practically sufficient photocatalytic activity, coating strength, and weather resistance can be achieved.
また、光触媒層の粒子間の隙間を十分確保することで、中間層に添加した有機防カビ剤の溶出が妨げられないため、光触媒の防藻、防カビ機能を補完するという目的を充分に果たすことが可能となる。 Also, by ensuring a sufficient gap between the particles of the photocatalyst layer, the elution of the organic antifungal agent added to the intermediate layer is not hindered, so that the purpose of complementing the photocatalytic antifungal and antifungal functions is sufficiently fulfilled. It becomes possible.
さらに、中間層に添加した紫外線吸収剤により下地の紫外線による劣化を抑制することが可能となる。 Further, the ultraviolet absorber added to the intermediate layer can suppress deterioration due to ultraviolet rays of the base.
上記したような種々の現象が同時に起こることで、中間層中の有機防カビ剤の分解を抑制し、防藻、防カビ性能を補完する有機防カビ剤の溶出も妨げることなく、かつ、中間層中の紫外線吸収剤により、耐候性、親水性、有害ガス分解性、耐光性、および所望の各種被膜特性（透明性、塗膜強度等）に優れた光触媒塗装体が実現されるものと考えられる。 By causing the various phenomena as described above to occur at the same time, the decomposition of the organic antifungal agent in the intermediate layer is suppressed, and the elution of the organic antifungal agent that complements the antialgae and antifungal properties is not hindered. It is thought that the photocatalyst coating body excellent in weather resistance, hydrophilicity, harmful gas decomposability, light resistance, and various desired film properties (transparency, film strength, etc.) is realized by the ultraviolet absorber in the layer. It is done.
基材
本発明に用いる基材は、その上に中間層が形成可能な材料であれば無機材料、有機材料を問わず種々の材料であってよく、その形状も限定されない。材料の観点からみた基材の好ましい例としては、金属、セラミック、ガラス、プラスチック、ゴム、石、セメント、コンクリ−ト、繊維、布帛、木、紙、それらの組合せ、それらの積層体、それらの表面に少なくとも一層の被膜を有するものが挙げられる。用途の観点からみた基材の好ましい例としては、建材、建物外装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装、交通標識、各種表示装置、広告塔、道路用遮音壁、鉄道用遮音壁、橋梁、ガードレ−ルの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー、ビニールハウス、車両用照明灯のカバー、屋外用照明器具、台及び上記物品表面に貼着させるためのフィルム、シート、シール等といった外装材全般が挙げられる。
Base Material The base material used in the present invention may be any material, regardless of inorganic material or organic material, as long as the intermediate layer can be formed thereon, and the shape is not limited. Preferred examples of the substrate from the viewpoint of materials include metals, ceramics, glass, plastics, rubber, stones, cement, concrete, fibers, fabrics, wood, paper, combinations thereof, laminates thereof, Examples thereof include those having at least one layer of coating on the surface. Preferred examples of base materials from the viewpoint of applications include building materials, building exteriors, window frames, window glass, structural members, exteriors and coatings of vehicles, exteriors of machinery and articles, dust covers and coatings, traffic signs, and various displays Equipment, advertising towers, sound insulation walls for roads, sound insulation walls for railways, bridges, guard rail exteriors and paintings, tunnel interiors and paintings, insulators, solar cell covers, solar water heater heat collection covers, plastic houses, vehicle lighting covers General exterior materials such as outdoor lighting fixtures, stands, and films, sheets, seals and the like for attaching to the article surface.
中間層およびそのための中間層コーティング液
中間層に用いられる樹脂は、有機防カビ剤および紫外線吸収剤の相溶性が良好で、基材との接着性、光触媒との接着性を有し、光触媒による中間層表面の劣化を抑制できるものであれば特に限定されず、樹脂中にポリシロキサンを含むシリコーン変性アクリル樹脂、シリコーン変性エポキシ樹脂、シリコーン変性ウレタン樹脂、シリコーン変性ポリエステル等のシリコーン変性樹脂が好適である。外装用建材に適用する場合には、シリコーン変性アクリル樹脂が耐候性の点からより好適である。シリコーン変性アクリル樹脂において、カルボキシル基を有するシリコーン変性アクリル樹脂とエポキシ基を有するシリコーン樹脂の二液を混合して使用することが、塗膜の強度を向上させる点からさらに好適である。
The resin used for the intermediate layer and the intermediate layer coating liquid intermediate layer has good compatibility with the organic antifungal agent and the ultraviolet absorber, has adhesion to the base material and adhesion to the photocatalyst, and depends on the photocatalyst. It is not particularly limited as long as it can suppress the deterioration of the intermediate layer surface, and silicone-modified resins such as silicone-modified acrylic resins, silicone-modified epoxy resins, silicone-modified urethane resins, and silicone-modified polyesters containing polysiloxane in the resin are suitable. is there. When applied to exterior building materials, silicone-modified acrylic resins are more suitable from the viewpoint of weather resistance. In the silicone-modified acrylic resin, it is more preferable to use a mixture of two liquids of a silicone-modified acrylic resin having a carboxyl group and a silicone resin having an epoxy group from the viewpoint of improving the strength of the coating film.
シリコーン変性樹脂は、ケイ素原子含有量が、シリコーン変性樹脂の固形分に対して０．２質量％以上１６．５質量％未満が好ましく、より好ましくは６．５質量％以上１６．５質量％未満である。シリコーン変性樹脂に含有されるケイ素原子含有量が０．２質量％未満の場合、すなわち有機樹脂成分が多い場合、中間層の耐候性が低下し、光触媒に侵食される可能性がある。またシリコーン変性樹脂に含有されるケイ素原子含有量が１６．５質量％以上の場合すなわちシリコーン成分が多い場合、中間層の性質が無機物により近づくため、耐候性は向上するが、逆に可とう性に乏しくなり、中間層にクラックが発生する場合がある。 In the silicone-modified resin, the silicon atom content is preferably 0.2% by mass or more and less than 16.5% by mass, more preferably 6.5% by mass or more and less than 16.5% by mass, based on the solid content of the silicone-modified resin. It is. When the silicon atom content contained in the silicone-modified resin is less than 0.2% by mass, that is, when the amount of the organic resin component is large, the weather resistance of the intermediate layer is lowered and the photocatalyst may be eroded. In addition, when the silicon atom content contained in the silicone-modified resin is 16.5% by mass or more, that is, when the silicone component is large, the properties of the intermediate layer are closer to the inorganic substance, so that the weather resistance is improved. The crack may occur in the intermediate layer.
前記シリコーン変性樹脂中のケイ素原子含有量は、Ｘ線光電子分光分析装置（ＸＰＳ）による化学分析によって測定することができる。測定機器および条件は当業者によって適宜選択できる。 The silicon atom content in the silicone-modified resin can be measured by chemical analysis using an X-ray photoelectron spectrometer (XPS). Measuring instruments and conditions can be appropriately selected by those skilled in the art.
中間層には、有機防カビ剤が添加される。本発明においては、中間層と相溶性が良好であればどのような有機防カビ剤でも使用することができる。例として、有機窒素硫黄系化合物、ピリチオン系化合物、有機ヨウ素系化合物、トリアジン系化合物、イソチアゾリン系化合物、イミダゾール系化合物、ピリジン系化合物、ニトリル系化合物、チオカーバメート系化合物、チアゾール系化合物、有機よう素化合物、ジスルフィド系化合物が挙げられ、単独もしくは混合物として用いられる。防カビ剤は一般に藻を防ぐ効果も合わせ持つものが多いことから、防カビ剤を添加することによって、カビと藻の両方を抑制することも期待できる。 An organic antifungal agent is added to the intermediate layer. In the present invention, any organic fungicide can be used as long as it has good compatibility with the intermediate layer. Examples include organic nitrogen sulfur compounds, pyrithione compounds, organic iodine compounds, triazine compounds, isothiazoline compounds, imidazole compounds, pyridine compounds, nitrile compounds, thiocarbamate compounds, thiazole compounds, organic iodine. Compounds and disulfide compounds may be mentioned and used alone or as a mixture. Since many antifungal agents generally have an effect of preventing algae, addition of the antifungal agent can be expected to suppress both mold and algae.
また防藻効果と防カビ効果を兼ねた有機防藻防カビ剤を中間層に添加しても同様な効果が得られる。 Further, the same effect can be obtained by adding an organic algal / antifungal agent that has both an algal and fungicidal effect to the intermediate layer.
有機防カビ剤の添加重量部は、有機防カビ剤メーカーが定める最適量あるいは、模擬的な防カビ試験を実施し、適宜決めてよい。 The addition part by weight of the organic antifungal agent may be determined as appropriate by carrying out an optimum amount determined by the organic antifungal agent manufacturer or a simulated antifungal test.
中間層には、紫外線吸収剤が添加される。本発明においては、中間層と相溶性が良好であればどのような紫外線吸収剤でも使用することができる。例として、ベンゾトリアゾール系化合物、ヒドロキシフェニルトリアジン系化合物、ベンゾエート系化合物、ベンゾフェノン系化合物などが挙げられ、単独もしくは混合物として用いられる。 An ultraviolet absorber is added to the intermediate layer. In the present invention, any ultraviolet absorber can be used as long as the compatibility with the intermediate layer is good. Examples include benzotriazole compounds, hydroxyphenyltriazine compounds, benzoate compounds, benzophenone compounds, and the like, which are used alone or as a mixture.
中間層には、その他に有機溶剤、着色顔料、体質顔料、顔料分散剤、消泡剤、酸化防止剤等の塗料用添加剤、塗料に通常含まれるその他成分を含有することができる。また、艶消し剤としてシリカ微粒子を含んでもよい。上記着色顔料としては特に限定されず、例えば、二酸化チタン、酸化鉄、カーボンブラック等の無機系顔料、フタロシアニン系、ベンズイミダゾロン系、イソインドリノン系、アゾ系、アンスラキノン系、キノフタロン系、アンスラピリジニン系、キナクリドン系、トルイジン系、ピラスロン系、ペリレン系等の有機系顔料を用いることができる。 In addition to the above, the intermediate layer may contain organic solvents, coloring pigments, extender pigments, pigment dispersants, antifoaming agents, additives for coatings such as antioxidants, and other components usually contained in coatings. Further, silica fine particles may be included as a matting agent. The color pigment is not particularly limited, and examples thereof include inorganic pigments such as titanium dioxide, iron oxide, and carbon black, phthalocyanine series, benzimidazolone series, isoindolinone series, azo series, anthraquinone series, quinophthalone series, anthra Organic pigments such as pyridinin, quinacridone, toluidine, pyrathrone, and perylene can be used.
本発明の中間層コーティング液は、前記したシリコーン変性樹脂、有機防カビ剤および紫外線吸収剤を溶媒中に分散させることにより得ることができる。溶媒としては、上記構成成分を適切に分散可能なあらゆる溶媒が使用可能であり、水および／または有機溶媒であってよい。また、本発明の中間層塗装用液剤の固形分濃度は特に限定されないが、１０〜２０質量％とするのが塗布し易い点で好ましい。なお、中間層コーティング液中の構成成分の分析は、樹脂成分に関しては、赤外分光分析で、有機防カビ剤成分については希釈後あるいは硬化させた後に、適切な溶媒で抽出し、ゲルパーミエーションクロマトグラフィーにて分析、スペクトルを解析することによって評価することができる。 The intermediate layer coating solution of the present invention can be obtained by dispersing the aforementioned silicone-modified resin, organic antifungal agent and ultraviolet absorber in a solvent. As the solvent, any solvent that can appropriately disperse the above-described constituent components can be used, and water and / or an organic solvent may be used. The solid content concentration of the intermediate layer coating solution of the present invention is not particularly limited, but it is preferably 10 to 20% by mass in terms of easy application. The analysis of the constituent components in the intermediate layer coating liquid is performed by infrared spectroscopic analysis for the resin component, and after being diluted or cured for the organic antifungal component, extracted with an appropriate solvent, and gel permeation. The analysis can be performed by chromatography and the spectrum can be analyzed.
中間層製造方法
本発明の中間層塗装体は、本発明の中間層コーティング液を、前記基材上に塗布することにより簡単に製造することができる。中間層の塗装方法は、前記液剤を刷毛塗り、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷等、一般に広く行われている方法を利用できる。コーティング液の基材への塗布後は、常温乾燥させればよく、あるいは必要に応じて加熱乾燥してもよい。
Intermediate Layer Manufacturing Method The intermediate layer coated body of the present invention can be easily manufactured by applying the intermediate layer coating liquid of the present invention onto the substrate. As a method for coating the intermediate layer, generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, and screen printing can be used. After applying the coating liquid to the substrate, it may be dried at room temperature, or may be heat-dried as necessary.
中間層の乾燥膜厚は特に限定されるものでは無いが、好ましくは１μｍ〜５０μｍ、より好ましくは１μｍ〜１０μｍである。１μｍより薄い場合は、光触媒による基材の劣化抑制効果が劣る可能性がある。５０μｍより厚い場合は、中間層の種類に依存するが、乾燥後に微細なクラックが発生する恐れがある。 Although the dry film thickness of an intermediate | middle layer is not specifically limited, Preferably they are 1 micrometer-50 micrometers, More preferably, they are 1 micrometer-10 micrometers. If it is thinner than 1 μm, the effect of suppressing deterioration of the substrate by the photocatalyst may be inferior. When it is thicker than 50 μm, although it depends on the type of the intermediate layer, there is a possibility that fine cracks may occur after drying.
光触媒層およびそのための光触媒コーティング液
本発明に用いる光触媒粒子は、光触媒活性を有する粒子であれば特に限定されず、あらゆる種類の光触媒の粒子が使用可能である。光触媒粒子の例としては、酸化チタン（チタニア）、ＺｎＯ、ＳｎＯ２、ＳｒＴｉＯ３、ＷＯ３、Ｂｉ２Ｏ３、Ｆｅ２Ｏ３のような金属酸化物の粒子が挙げられ、好ましくは酸化チタン粒子、より好ましくはアナターゼ型酸化チタン粒子である。酸化チタンは、無害で、化学的にも安定で、かつ、安価に入手可能である。また、酸化チタンはバンドギャップエネルギーが高く、従って、光励起には紫外線を必要とし、光励起の過程で可視光を吸収しないので、補色成分による発色が起こらない。酸化チタンは、粉末状、ゾル状、溶液状など様々な形態で入手可能であるが、光触媒活性を示すものであれば、いずれの形態でも使用可能である。
Photocatalyst layer and photocatalyst coating liquid therefor The photocatalyst particles used in the present invention are not particularly limited as long as they have particles having photocatalytic activity, and any kind of photocatalyst particles can be used. Examples of the photocatalyst particles include metal oxide particles such as titanium oxide (titania), ZnO, SnO 2 , SrTiO 3 , WO 3 , Bi 2 O 3 , Fe 2 O 3 , and preferably titanium oxide particles. More preferred are anatase-type titanium oxide particles. Titanium oxide is harmless, chemically stable, and available at low cost. Titanium oxide has a high band gap energy, and therefore requires ultraviolet light for photoexcitation and does not absorb visible light in the process of photoexcitation, so that no color formation due to a complementary color component occurs. Titanium oxide is available in various forms such as powder, sol, and solution, but any form can be used as long as it exhibits photocatalytic activity.
本発明の好ましい態様によれば、光触媒粒子が１０ｎｍ以上１００ｎｍ以下の平均粒径を有するのが好ましく、より好ましくは１０ｎｍ以上６０ｎｍ以下である。なお、この平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が最も良いが、略円形や楕円形でも良く、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。この範囲内であると、耐候性、有害ガス分解性、および所望の各種被膜特性（透明性、塗膜強度等）が効率良く発揮される。 According to a preferred embodiment of the present invention, the photocatalyst particles preferably have an average particle size of 10 nm to 100 nm, more preferably 10 nm to 60 nm. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope. As the shape of the particle, a true sphere is the best, but it may be approximately circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2). Within this range, weather resistance, harmful gas decomposability, and various desired coating properties (transparency, coating strength, etc.) are efficiently exhibited.
本発明の光触媒層およびコーティング液における光触媒粒子の含有量は、光触媒粒子、無機酸化物粒子、および加水分解性シリコーンの合計量１００質量部に対して、１質量部以上２０質量部未満、好ましくは３質量部以上１５質量部以下であり、より好ましくは５質量部以上１０質量部以下である。このように光触媒粒子の配合割合を少なくすることで、光触媒粒子の中間層との直接的な接触を最小限に抑えることができ、それにより中間層に対する浸食を防止することができ、耐候性も向上すると考えられる。それにもかかわらず、有害ガス分解性などの光触媒活性に起因する機能も十分に発揮させることができる。 The content of the photocatalyst particles in the photocatalyst layer and the coating liquid of the present invention is 1 part by mass or more and less than 20 parts by mass, preferably 100 parts by mass of the total amount of photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone, preferably 3 parts by mass or more and 15 parts by mass or less, more preferably 5 parts by mass or more and 10 parts by mass or less. By reducing the blending ratio of the photocatalyst particles in this way, it is possible to minimize the direct contact of the photocatalyst particles with the intermediate layer, thereby preventing erosion of the intermediate layer and weather resistance. It is thought to improve. Nevertheless, functions resulting from photocatalytic activity such as harmful gas decomposability can be sufficiently exhibited.
本発明の好ましい態様によれば、さらに高い光触媒能を発現するために、バナジウム、鉄、コバルト、ニッケル、パラジウム、亜鉛、ルテニウム、ロジウム、鉛、銅、銀、白金および金からなる群より選ばれる少なくとも一種の金属および／またはその金属からなる金属化合物を、光触媒層や光触媒コーティング液に添加することができる。この添加は、前記金属または金属化合物をコーティング液に混合し、溶解または分散させる方法、前記金属または金属化合物を光触媒層や光触媒粒子に担持する方法、などのいずれの方法によっても行うことができる。 According to a preferred embodiment of the present invention, the material is selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, lead, copper, silver, platinum, and gold in order to develop higher photocatalytic activity. At least one metal and / or a metal compound comprising the metal can be added to the photocatalyst layer or the photocatalyst coating liquid. This addition can be performed by any method such as a method in which the metal or metal compound is mixed and dissolved or dispersed in a coating solution, or a method in which the metal or metal compound is supported on a photocatalyst layer or photocatalyst particles.
本発明に用いる無機酸化物粒子は、光触媒粒子と共に層を形成可能な無機酸化物の粒子であれば特に限定されず、あらゆる種類の無機酸化物の粒子が使用可能である。そのような無機酸化物粒子の例としては、シリカ、アルミナ、ジルコニア、セリア、イットリア、ボロニア、マグネシア、カルシア、フェライト、無定型チタニア、ハフニア等の単一酸化物の粒子；およびチタン酸バリウム、ケイ酸カルシウム等の複合酸化物の粒子が挙げられ、より好ましくはシリカ粒子である。これら無機酸化物粒子は、水を分散媒とした水性コロイド；またはエチルアルコール、イソプロピルアルコール、もしくはエチレングリコールなどの親水性溶媒にコロイド状に分散させたオルガノゾルの形態であるのが好ましく、特に好ましくはコロイダルシリカである。 The inorganic oxide particles used in the present invention are not particularly limited as long as they are inorganic oxide particles capable of forming a layer together with photocatalyst particles, and any kind of inorganic oxide particles can be used. Examples of such inorganic oxide particles include single oxide particles such as silica, alumina, zirconia, ceria, yttria, boronia, magnesia, calcia, ferrite, amorphous titania, hafnia; and barium titanate, silica The particle | grains of complex oxides, such as calcium acid, are mentioned, More preferably, it is a silica particle. These inorganic oxide particles are preferably in the form of an aqueous colloid using water as a dispersion medium; or an organosol dispersed in a hydrophilic solvent such as ethyl alcohol, isopropyl alcohol, or ethylene glycol, and particularly preferably. Colloidal silica.
本発明の好ましい態様によれば、無機酸化物粒子が、５ｎｍを超え４０ｎｍ未満の平均粒径を有するのが好ましく、より好ましくは１０ｎｍ以上４０ｎｍ未満、さらに好ましくは１０ｎｍ以上３０ｎｍ以下である。５ｎｍ以下では、無機酸化物粒子の分散性が不安定となり、小粒径にもかかわらず透明性が低下する場合がある。また４０ｎｍ以上の場合は中間層との密着性が損なわれる場合がある。なお、この平均粒径は、走査型電子顕微鏡により２０万倍の視野に入る任意の１００個の粒子の長さを測定した個数平均値として算出される。粒子の形状としては真球が最も良いが、略円形や楕円形でも良く、その場合の粒子の長さは（（長径＋短径）／２）として略算出される。この範囲内であると、耐候性、有害ガス分解性、および所望の各種被膜特性（透明性、塗膜強度等）が効率良く発揮される。 According to a preferred embodiment of the present invention, the inorganic oxide particles preferably have an average particle size of more than 5 nm and less than 40 nm, more preferably 10 nm or more and less than 40 nm, still more preferably 10 nm or more and 30 nm or less. If it is 5 nm or less, the dispersibility of the inorganic oxide particles becomes unstable, and the transparency may be lowered despite the small particle size. Moreover, in the case of 40 nm or more, the adhesiveness with the intermediate layer may be impaired. The average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope. As the shape of the particle, a true sphere is the best, but it may be approximately circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2). Within this range, weather resistance, harmful gas decomposability, and various desired coating properties (transparency, coating strength, etc.) are efficiently exhibited.
本発明の光触媒層およびコーティング液における無機酸化物粒子の含有量は、光触媒粒子、無機酸化物粒子、および加水分解性シリコーンの合計量１００質量部に対して、７０質量部を超え９９質量部以下であり、好ましくは８０質量部以上９７質量部以下であり、より好ましくは８５質量部以上９５質量部以下、さらに好ましくは９０質量部以上９５質量部以下である。 The content of the inorganic oxide particles in the photocatalyst layer and the coating liquid of the present invention is more than 70 parts by mass and 99 parts by mass or less with respect to 100 parts by mass of the total amount of photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone. Preferably, it is 80 to 97 mass parts, More preferably, it is 85 to 95 mass parts, More preferably, it is 90 to 95 mass parts.
本発明の光触媒層は加水分解性シリコーンを実質的に含まないのが好ましく、より好ましくは全く含まない。加水分解性シリコーンとは、アルコキシ基を有するオルガノシロキサンおよび／またはその部分加水分解縮合物の総称である。しかしながら、本発明の有害ガス分解性を確保できる程度であれば加水分解性シリコーンを任意成分として含有することは許容される。したがって、加水分解性シリコーンの含有量は、シリカ換算で、光触媒粒子、無機酸化物粒子、および加水分解性シリコーンの合計量１００質量部に対して、０質量部以上１０質量部未満であり、好ましくは５質量部以下、最も好ましくは０質量部である。加水分解性シリコーンとしては、４官能シリコーン化合物がよく使用され、例えば、エチルシリケート４０（オリゴマー、Ｒがエチル基）、エチルシリケート４８（オリゴマー、Ｒがエチル基）メチルシリケート５１（オリゴマー、Ｒがメチル基）（いずれもコルコート社製）の形で市販されている。 The photocatalyst layer of the present invention preferably contains substantially no hydrolyzable silicone, and more preferably does not contain at all. The hydrolyzable silicone is a general term for an organosiloxane having an alkoxy group and / or a partially hydrolyzed condensate thereof. However, it is allowed to contain hydrolyzable silicone as an optional component as long as the harmful gas decomposability of the present invention can be ensured. Therefore, the content of the hydrolyzable silicone is 0 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the total amount of the photocatalyst particles, the inorganic oxide particles, and the hydrolyzable silicone in terms of silica. Is 5 parts by mass or less, and most preferably 0 part by mass. As the hydrolyzable silicone, a tetrafunctional silicone compound is often used. For example, ethyl silicate 40 (oligomer, R is an ethyl group), ethyl silicate 48 (oligomer, R is an ethyl group), methyl silicate 51 (oligomer, R is a methyl group) Group) (both manufactured by Colcoat Co.).
光触媒コーティング液には任意成分として界面活性剤を含んでよい。本発明に用いる界面活性剤は、光触媒粒子、無機酸化物粒子、および加水分解性シリコーンの合計量１００質量部に対して、０質量部以上１０質量部未満光触媒層に含有されていてもよく、好ましくは０質量部以上８質量部以下であり、より好ましくは０以上６質量部以下である。界面活性剤の効果の１つとして基材へのレベリング性があり、コーティング液と基材との組合せによって界面活性剤の量を先述の範囲内で適宜決めれば良く、その際の下限値は０．１質量部とされてよい。この界面活性剤は光触媒コーティング液の濡れ性を改善するために有効な成分であるが、塗布後に形成される光触媒層にあってはもはや本発明の光触媒塗装体の効果には寄与しない不可避不純物に相当する。したがって、光触媒コーティング液に要求される濡れ性に応じて、上記含有量範囲内において使用されてよく、濡れ性を問題にしないのであれば界面活性剤は実質的にあるいは一切含まなくてよい。使用すべき界面活性剤は、光触媒や無機酸化物粒子の分散安定性、中間層上に塗布した際の濡れ性を勘案し適宜選択されることができるが、非イオン性界面活性剤が好ましく、より好ましくは、エーテル型非イオン性界面活性剤、エステル型非イオン性界面活性剤、ポリアルキレングリコール非イオン性界面活性剤、フッ素系非イオン性界面活性剤、シリコン系非イオン性界面活性剤が挙げられる。 The photocatalyst coating liquid may contain a surfactant as an optional component. The surfactant used in the present invention may be contained in the photocatalyst layer in an amount of 0 to less than 10 parts by mass with respect to 100 parts by mass of the total amount of photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone, Preferably they are 0 mass part or more and 8 mass parts or less, More preferably, they are 0 or more and 6 mass parts or less. One of the effects of the surfactant is leveling to the substrate, and the amount of the surfactant may be appropriately determined within the above-mentioned range depending on the combination of the coating liquid and the substrate, and the lower limit at that time is 0 It may be 1 part by mass. This surfactant is an effective component for improving the wettability of the photocatalyst coating solution, but in the photocatalyst layer formed after coating, it is an inevitable impurity that no longer contributes to the effect of the photocatalyst-coated body of the present invention. Equivalent to. Therefore, it may be used within the above-mentioned content range depending on the wettability required for the photocatalyst coating liquid, and if the wettability is not a problem, the surfactant may be contained substantially or not at all. The surfactant to be used can be appropriately selected in consideration of the dispersion stability of the photocatalyst and inorganic oxide particles, and wettability when applied on the intermediate layer, but a nonionic surfactant is preferable, More preferably, an ether type nonionic surfactant, an ester type nonionic surfactant, a polyalkylene glycol nonionic surfactant, a fluorine-based nonionic surfactant, or a silicon-based nonionic surfactant is used. Can be mentioned.
本発明の光触媒コーティング液は、光触媒粒子、無機酸化物粒子、および所望により加水分解性シリコーンおよび界面活性剤を上記特定の配合比率で溶媒中に分散させることにより得ることができる。溶媒としては、上記構成成分を適切に分散可能なあらゆる溶媒が使用可能であり、水および／または有機溶媒であってよい。また、本発明の光触媒コーティング液の固形分濃度は特に限定されないが、１〜１０質量％とするのが塗布し易い点で好ましい。なお、光触媒コーティング組成物中の構成成分の分析は、コーティング液を限外ろ過によって粒子成分と濾液に分離し、それぞれを赤外分光分析、ゲルパーミエーションクロマトグラフィー、蛍光Ｘ線分光分析などで分析し、スペクトルを解析することによって評価することができる。 The photocatalyst coating liquid of the present invention can be obtained by dispersing photocatalyst particles, inorganic oxide particles, and optionally hydrolyzable silicone and a surfactant in the above-mentioned specific mixing ratio in a solvent. As the solvent, any solvent that can appropriately disperse the above-described constituent components can be used, and water and / or an organic solvent may be used. Moreover, the solid content concentration of the photocatalyst coating liquid of the present invention is not particularly limited, but it is preferably 1 to 10% by mass because it is easy to apply. The components in the photocatalyst coating composition are analyzed by separating the coating solution into particle components and filtrate by ultrafiltration, and analyzing each by infrared spectroscopic analysis, gel permeation chromatography, fluorescent X-ray spectroscopic analysis, etc. It can be evaluated by analyzing the spectrum.
本発明の光触媒層は、０．５μｍ以上３．０μｍ以下の膜厚を有し、好ましくは１．０μｍ以上２．０μｍ以下である。このような範囲内であると、光触媒層と中間層の界面に到達する紫外線が減衰されるので耐光性が向上する。また、無機酸化物粒子よりも含有比率が低い光触媒粒子を膜厚方向に増加させることができるので、有害ガス分解性も向上する。さらには、透明性においても優れた特性が得られる。 The photocatalyst layer of the present invention has a film thickness of 0.5 μm or more and 3.0 μm or less, preferably 1.0 μm or more and 2.0 μm or less. Within such a range, the ultraviolet light reaching the interface between the photocatalyst layer and the intermediate layer is attenuated, so that the light resistance is improved. Moreover, since the photocatalyst particles having a lower content ratio than the inorganic oxide particles can be increased in the film thickness direction, harmful gas decomposability is also improved. Furthermore, excellent characteristics can be obtained in terms of transparency.
光触媒層製造方法
本発明の光触媒塗装体は、本発明の光触媒コーティング液を、前記中間層を有する基材上に塗布することにより簡単に製造することができる。光触媒層の塗装方法は、前記液剤を刷毛塗り、ローラー、スプレー、ロールコーター、フローコーター、ディップコート、流し塗り、スクリーン印刷等、一般に広く行われている方法を利用できる。コーティング液の基材への塗布後は、常温乾燥させればよく、あるいは必要に応じて加熱乾燥してもよい。
Photocatalyst layer manufacturing method The photocatalyst coating body of this invention can be easily manufactured by apply | coating the photocatalyst coating liquid of this invention on the base material which has the said intermediate | middle layer. As a method for coating the photocatalyst layer, generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, and screen printing can be used. After applying the coating liquid to the substrate, it may be dried at room temperature, or may be heat-dried as necessary.
本発明を以下の例に基づいて具体的に説明するが、本発明はこれらの例に限定されるものではない。
なお、以下の例において中間層コーティング液は、以下に示したいずれかのシリコーン変性アクリル樹脂材と水と造膜助剤を適宜混合して作製した。詳細を表１に示した。
・ケイ素原子含有量が、シリコーン変性樹脂の固形分に対して１０質量％のシリコーン変性アクリル樹脂ディスパージョン
・ケイ素原子含有量が、シリコーン変性樹脂の固形分に対して０．２質量％のシリコーン変性アクリル樹脂ディスパージョン
・ケイ素原子含有量が、シリコーン変性樹脂の固形分に対して１６．５質量％のシリコーン変性アクリル樹脂ディスパージョン
The present invention will be specifically described based on the following examples, but the present invention is not limited to these examples.
In the following examples, the intermediate layer coating solution was prepared by appropriately mixing one of the following silicone-modified acrylic resin materials, water, and a film-forming aid. Details are shown in Table 1.
Silicone-modified acrylic resin dispersion having a silicon atom content of 10% by mass with respect to the solid content of the silicone-modified resin. Silicone modification having a silicon atom content of 0.2% by mass with respect to the solid content of the silicone-modified resin. Acrylic resin dispersion ・ Silicone-modified acrylic resin dispersion having a silicon atom content of 16.5% by mass based on the solid content of the silicone-modified resin.
防カビ剤は、市販の窒素硫黄系化合物とトリアジン系化合物からなるものを用い、防カビ剤の濃度は中間層コーティング液に対し０．５質量％とした。 As the fungicide, a commercially available nitrogen-sulfur compound and a triazine compound were used, and the concentration of the fungicide was 0.5% by mass with respect to the intermediate layer coating solution.
紫外線吸収剤は、市販のヒドロキシフェニルトリアジン系化合物からなるものを用い、その濃度は中間層コーティング液に対し１質量％とした。 As the ultraviolet absorber, a commercially available hydroxyphenyl triazine compound was used, and its concentration was 1% by mass with respect to the intermediate layer coating solution.
以下の例において光触媒層コーティング液は、以下に示した光触媒粒子と、いずれかの無機酸化物と水と界面活性剤を適宜混合して作製した。詳細を表２に示した。
光触媒粒子
・チタニア水分散体（平均粒径：４２ｎｍ、塩基性）
無機酸化物粒子
・水分散型コロイダルシリカ（平均粒径：２６ｎｍ、塩基性）
・水分散型コロイダルシリカ（平均粒径：１４ｎｍ、塩基性）
・水分散型コロイダルシリカ（平均粒径：５ｎｍ、塩基性）
・水分散型コロイダルシリカ（平均粒径：５１ｎｍ、塩基性）
加水分解性シリコーン
・テトラメトキシシランの重縮合物（ＳｉＯ２換算濃度：５１質量％。溶媒：メタノール、水）
界面活性剤
・ポリエーテル変性シリコーン系界面活性剤
In the following examples, the photocatalyst layer coating liquid was prepared by appropriately mixing the photocatalyst particles shown below, any inorganic oxide, water, and a surfactant. Details are shown in Table 2.
Photocatalyst particles / titania water dispersion (average particle size: 42 nm, basic)
Inorganic oxide particles / water-dispersed colloidal silica (average particle size: 26 nm, basic)
・ Water-dispersed colloidal silica (average particle size: 14 nm, basic)
・ Water-dispersed colloidal silica (average particle size: 5 nm, basic)
・ Water-dispersed colloidal silica (average particle size: 51 nm, basic)
Hydrocondensable silicone / tetramethoxysilane polycondensate (SiO 2 equivalent concentration: 51 mass%, solvent: methanol, water)
Surfactant / polyether modified silicone surfactant
例１〜８：ガス分解性の評価
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロート板ガラスを用意した。あらかじめ加熱したガラス基材上に、表１のＭ−１に記載の中間層コーティング液をスプレーコートし、１２０℃で乾燥し中間層を得た。このＭ−１液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、例１〜８のいずれの例においても約１０μｍであった。
Examples 1 to 8: Evaluation of gas decomposability A photocatalyst-coated body provided with an intermediate layer and a photocatalyst layer was produced as follows. First, a float plate glass was prepared as a base material. On the glass substrate heated beforehand, the intermediate | middle layer coating liquid as described in M-1 of Table 1 was spray-coated, and it dried at 120 degreeC, and obtained the intermediate | middle layer. The solid content concentration of the resin in this M-1 solution was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm in any of Examples 1 to 8.
一方、光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカと、溶媒として水とを表２のＴ−１〜Ｔ−８に示される配合比で混合して、光触媒コーティング液を得た。光触媒コーティング液中の、光触媒、無機酸化物および加水分解性シリコーンの合計の固形分濃度は５．５質量％とした。得られた光触媒コーティング液をあらかじめ加熱した上記中間層塗装体上にスプレー塗布し、１２０℃で乾燥した。走査型電子顕微鏡観察により光触媒層の膜厚を測定したところ、例１〜８のいずれの例においても約０．５μｍであった。こうして、中間層と光触媒層を形成させて、光触媒塗装体を得た。 On the other hand, a titania aqueous dispersion as a photocatalyst, a water-dispersed colloidal silica as an inorganic oxide, and water as a solvent are mixed at a blending ratio shown by T-1 to T-8 in Table 2 to form a photocatalytic coating. A liquid was obtained. The total solid content concentration of the photocatalyst, the inorganic oxide, and the hydrolyzable silicone in the photocatalyst coating liquid was 5.5% by mass. The obtained photocatalyst coating liquid was spray-coated on the intermediate layer-coated body heated in advance and dried at 120 ° C. When the film thickness of the photocatalyst layer was measured by observation with a scanning electron microscope, it was about 0.5 μm in any of Examples 1 to 8. Thus, an intermediate layer and a photocatalyst layer were formed to obtain a photocatalyst-coated body.
こうして得られた５０×１００ｍｍの大きさの光触媒塗装体について、以下の通りガス分解性試験を行った。光触媒塗装体に前処理として１ｍＷ／ｃｍ２のＢＬＢ光で１２ｈｒ以上照射した。ＪＩＳ Ｒ１７０１に記載の反応容器内に塗装体サンプルを１枚セットした。２５℃、５０％ＲＨに調整した空気に約１０００ｐｐｂになるようにＮＯガスを混合し、遮光した反応容器内に２０分導入した。その後ガスを導入したままで３ｍＷ／ｃｍ２に調整したＢＬＢ光を２０分間照射した。その後ガスを導入した状態で再度反応容器を遮光した。ＮＯｘ除去量は、ＢＬＢ光照射前後でのＮＯ、ＮＯ２濃度から下記の式に従って計算した。
ＮＯｘ除去量＝［ＮＯ（照射後）−ＮＯ（照射時）］−［ＮＯ２（照射時）−ＮＯ２（照射後）］
The photocatalyst-coated body having a size of 50 × 100 mm thus obtained was subjected to a gas decomposability test as follows. As a pretreatment, the photocatalyst-coated body was irradiated with 1 mW / cm 2 of BLB light for 12 hours or more. One coated body sample was set in the reaction vessel described in JIS R1701. NO gas was mixed with air adjusted to 25 ° C. and 50% RH so as to be about 1000 ppb, and introduced into a light-shielded reaction vessel for 20 minutes. Thereafter, BLB light adjusted to 3 mW / cm 2 was irradiated for 20 minutes while the gas was introduced. Thereafter, the reaction vessel was shielded from light again with the gas introduced. The NOx removal amount was calculated according to the following formula from the NO and NO 2 concentrations before and after the BLB light irradiation.
NOx removal amount = [NO (after irradiation) −NO (at irradiation)] − [NO 2 (at irradiation) −NO 2 (after irradiation)]
得られた結果は表３に示される通りであった。表３に示されるように、光触媒層を光触媒粒子と無機酸化物から構成し、加水分解性シリコーンを含まない構造にすると、良好なＮＯｘ分解性を示した。一方、加水分解性シリコーンが１０質量部入ったものは、ＮＯｘ分解性が喪失していることが分かった。また光触媒層中の光触媒比率を２．５倍に増やしてもその傾向は変わらなかった。 The obtained results were as shown in Table 3. As shown in Table 3, when the photocatalyst layer was composed of photocatalyst particles and an inorganic oxide and did not contain hydrolyzable silicone, good NOx decomposability was exhibited. On the other hand, those containing 10 parts by mass of hydrolyzable silicone were found to lose NOx decomposability. Moreover, even if the photocatalyst ratio in the photocatalyst layer was increased 2.5 times, the tendency was not changed.
例９、１０：防藻性の評価
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロート板ガラスを用意した。あらかじめ加熱したガラス基材上に、表１のＭ−１およびＭ−２に記載の中間層コーティング液をスプレーコートし、１２０℃で乾燥し中間層を得た。Ｍ−１およびＭ−２液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、例９、１０のいずれの例においても約１０μｍであった。
Examples 9 and 10: Evaluation of anti-algae properties A photocatalyst-coated body provided with an intermediate layer and a photocatalyst layer was produced as follows. First, a float plate glass was prepared as a base material. On the glass substrate heated beforehand, the intermediate | middle layer coating liquid as described in M-1 and M-2 of Table 1 was spray-coated, and it dried at 120 degreeC, and obtained the intermediate | middle layer. The solid content concentration of the resin in the liquids M-1 and M-2 was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm in any of Examples 9 and 10.
一方、光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカと、溶媒として水とを表２のＴ−４に示される配合比で混合して、光触媒コーティング液を得た。光触媒コーティング液中の光触媒および無機酸化物の合計の固形分濃度は５．５質量％とした。得られた光触媒コーティング液をあらかじめ加熱した上記中間層塗装体上にスプレー塗布し、１２０℃で乾燥した。走査型電子顕微鏡観察により光触媒層の膜厚を測定したところ、例９、１０のいずれの例においても約０．５μｍであった。こうして、中間層と光触媒層を形成させて、光触媒塗装体を得た。 On the other hand, a titania aqueous dispersion as a photocatalyst, a water-dispersed colloidal silica as an inorganic oxide, and water as a solvent were mixed at a mixing ratio shown by T-4 in Table 2 to obtain a photocatalyst coating solution. . The total solid concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating solution was 5.5% by mass. The obtained photocatalyst coating liquid was spray-coated on the intermediate layer-coated body heated in advance and dried at 120 ° C. When the film thickness of the photocatalyst layer was measured by observation with a scanning electron microscope, it was about 0.5 μm in any of Examples 9 and 10. Thus, an intermediate layer and a photocatalyst layer were formed to obtain a photocatalyst-coated body.
こうして得られた５０×５０ｍｍの大きさの光触媒塗装体について、以下の通り防藻性試験を行った。藻の代用としてクロレラ（ＮＩＥＳ−６４２）を用いた。試験中のクロレラの栄養源として無機塩培地を使用した。シャーレ内に、光触媒塗装体をおき一定量のクロレラと無機塩培地を含む水を投入し、蓋をして温度２５℃±２℃の条件下で、照度４０００ｌｘの蛍光灯下で培養した。なおシャーレと蛍光灯の間に透明なアクリル板を挟み、紫外線を完全に遮断した。クロレラの繁殖は目視にて比較、判定した。 The photocatalyst-coated body having a size of 50 × 50 mm obtained in this way was subjected to an algal control test as follows. Chlorella (NIES-642) was used as a substitute for algae. Inorganic salt medium was used as a nutrient source for chlorella during the test. A photocatalyst-coated body was placed in the petri dish, and water containing a certain amount of chlorella and an inorganic salt medium was placed. The lid was covered and cultured under a fluorescent lamp with an illuminance of 4000 lx under a temperature of 25 ° C. ± 2 ° C. A transparent acrylic plate was sandwiched between the petri dish and the fluorescent lamp to completely block ultraviolet rays. Chlorella reproduction was compared and judged visually.
得られた結果は表４に示される通りであった。ここで、表中の○は目視で藻の発生が認められなかったもの、×は目視で藻の発生が認められたものを表す。表４に示されるように、光触媒層を光触媒粒子と無機酸化物から構成し、実質的に加水分解性シリコーンを含まないことにより紫外線が全く無い状況においても良好な防藻性能を示すことから、光触媒の防藻、防カビ機能を補完するという目的を充分に果たせることが分かった。 The obtained results were as shown in Table 4. Here, ○ in the table indicates that no algae were visually observed, and x indicates that algae was visually observed. As shown in Table 4, the photocatalyst layer is composed of photocatalyst particles and an inorganic oxide, and since it does not contain hydrolyzable silicone, it exhibits good antialgae performance even in the absence of ultraviolet rays. It was found that the objective of supplementing the photocatalytic anti-algae and anti-fungal functions could be fulfilled sufficiently.
例１１〜１３：塗膜の透明性評価
光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロート板ガラスを用意した。光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカと、溶媒として水とを表２のＴ−４、Ｔ−９、１０に示される配合比で混合して、光触媒コーティング液を得た。光触媒コーティング液中の光触媒および無機酸化物の合計の固形分濃度は５．５質量％とした。得られた光触媒コーティング液を５０×５０ｍｍの板ガラス上に１ｇ滴下した後、１０００ｒｐｍ１０秒の条件でスピンコートして塗膜の透明性試験体を得た。
Examples 11 to 13: Evaluation of transparency of coating film A photocatalyst-coated body provided with a photocatalyst layer was produced as follows. First, a float plate glass was prepared as a base material. A titania aqueous dispersion as a photocatalyst, a water-dispersed colloidal silica as an inorganic oxide, and water as a solvent are mixed at a blending ratio indicated by T-4, T-9 and 10 in Table 2 to form a photocatalyst coating A liquid was obtained. The total solid concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating solution was 5.5% by mass. After 1 g of the obtained photocatalyst coating liquid was dropped on a 50 × 50 mm plate glass, it was spin-coated under the condition of 1000 rpm for 10 seconds to obtain a coating film transparency test body.
こうして得られた５０×５０ｍｍの大きさの光触媒塗装体について、ＢＹＫ−Ｇａｒｄｎｅｒ社製ｈａｚｅ−ｇａｒｄ ｐｌｕｓにてヘイズ値を測定した。 About the photocatalyst coating body of the magnitude | size of 50x50 mm obtained in this way, the haze value was measured in BYK-Gardner company make-gard plus.
得られた結果は表５に示される通りであった。表５より、例１１、１２の光触媒塗装体はヘイズ値を１％未満に抑えることができ、透明性が確保できることが分かった。 The results obtained were as shown in Table 5. From Table 5, it was found that the photocatalyst-coated bodies of Examples 11 and 12 were able to suppress the haze value to less than 1% and ensure transparency.
例１４〜１６：塗膜の密着性評価
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロートガラス板に汎用のエポキシ樹脂系の下塗り剤を塗装し、乾燥したものを用意した。あらかじめ加熱したガラス基材上に、表１のＭ−１に記載の中間層コーティング液をスプレーコートし、１２０℃で乾燥し中間層を得た。Ｍ−１液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、例１４〜１６のいずれの例においても約１０μｍであった。
Examples 14 to 16: Evaluation of coating film adhesion A photocatalyst-coated body provided with an intermediate layer and a photocatalyst layer was produced as follows. First, a general-purpose epoxy resin-based primer was applied to a float glass plate as a base material and dried. On the glass substrate heated beforehand, the intermediate | middle layer coating liquid as described in M-1 of Table 1 was spray-coated, and it dried at 120 degreeC, and obtained the intermediate | middle layer. The solid content concentration of the resin in the M-1 solution was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm in any of Examples 14 to 16.
一方、光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカと、溶媒として水とを表２のＴ−４、Ｔ−９およびＴ−１１に示される配合比で混合して、光触媒コーティング液を得た。光触媒コーティング液中の光触媒および無機酸化物の合計の固形分濃度は５．５質量％とした。得られた光触媒コーティング液をあらかじめ加熱した上記中間層塗装体上にスプレー塗布し、１２０℃で乾燥した。走査型電子顕微鏡観察により光触媒層の膜厚を測定したところ、例１４〜１６のいずれの例においても約０．５μｍであった。こうして、中間層と光触媒層を形成させて、光触媒塗装体を得た。 On the other hand, a titania aqueous dispersion as a photocatalyst, a water-dispersed colloidal silica as an inorganic oxide, and water as a solvent are mixed in a mixing ratio shown in T-4, T-9 and T-11 in Table 2. Thus, a photocatalyst coating solution was obtained. The total solid concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating solution was 5.5% by mass. The obtained photocatalyst coating liquid was spray-coated on the intermediate layer-coated body heated in advance and dried at 120 ° C. When the film thickness of the photocatalyst layer was measured by observation with a scanning electron microscope, it was about 0.5 μm in any of Examples 14 to 16. Thus, an intermediate layer and a photocatalyst layer were formed to obtain a photocatalyst-coated body.
こうして得られた５０×５０ｍｍの大きさの光触媒塗装体について、常温の飽和水酸化カルシウム水溶液中に１８時間浸漬した。水洗い後、５０℃で１時間乾燥させた後、塗膜表面にＪＩＳ Ｚ１５２２に規定されるセロハンテープを貼り、垂直に瞬間的に剥がしたあと、剥離面を観察して、前後での膜の残存を確認した。 The photocatalyst-coated body having a size of 50 × 50 mm obtained in this way was immersed in a saturated aqueous calcium hydroxide solution at room temperature for 18 hours. After washing with water and drying at 50 ° C. for 1 hour, a cellophane tape specified in JIS Z1522 is applied to the surface of the coating film, peeled off instantaneously in a vertical direction, the peeled surface is observed, and the film remains before and after It was confirmed.
得られた結果は表６に示される通りであった。ここで表中の○は光触媒層の剥離が全く認められなかったもの、△は光触媒層の剥離が一部認められたものを表す。例１４、１５の光触媒塗装体は、光触媒層が中間層に対し十分な密着性を有することが分かった。 The obtained results were as shown in Table 6. Here, ○ in the table indicates that no photocatalyst layer peeling was observed, and Δ indicates that some photocatalyst layer peeling was observed. It turned out that the photocatalyst coating body of Examples 14 and 15 has sufficient adhesiveness with respect to an intermediate | middle layer.
例１７〜２３：塗膜の耐候性評価−１
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロート板ガラスを用意した。あらかじめ加熱したガラス基材上に、表１のＭ−３に記載の中間層コーティング液に着色顔料を混合したものをスプレーコートし、１２０℃で乾燥し中間層を得た。Ｍ−３液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、例１７〜２３のいずれの例においても約１０μｍであった。
Examples 17 to 23: Evaluation of weather resistance of coating film-1
The photocatalyst coating body provided with the intermediate | middle layer and the photocatalyst layer was manufactured as follows. First, a float plate glass was prepared as a base material. On the glass substrate heated beforehand, what mixed the color pigment with the intermediate | middle layer coating liquid of M-3 of Table 1 was spray-coated, and it dried at 120 degreeC, and obtained the intermediate | middle layer. The solid content concentration of the resin in the M-3 solution was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm in any of Examples 17-23.
一方、光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカと、溶媒として水とを表２のＴ−１〜Ｔ−４、Ｔ−６、Ｔ−１２、Ｔ−１３に示される配合比で混合して、光触媒コーティング液を得た。光触媒コーティング液中の光触媒および無機酸化物の合計の固形分濃度は５．５質量％とした。得られた光触媒コーティング液をあらかじめ加熱した上記中間層塗装体上にスプレー塗布し、１２０℃で乾燥した。走査型電子顕微鏡観察により光触媒層の膜厚を測定したところ、例１７〜２３のいずれの例においても約０．５μｍであった。こうして、中間層と光触媒層を形成させて、光触媒塗装体を得た。 On the other hand, titania aqueous dispersion as a photocatalyst, water-dispersed colloidal silica as an inorganic oxide, and water as a solvent are T-1 to T-4, T-6, T-12, and T-13 in Table 2. To obtain a photocatalyst coating liquid. The total solid concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating solution was 5.5% by mass. The obtained photocatalyst coating liquid was spray-coated on the intermediate layer-coated body heated in advance and dried at 120 ° C. When the film thickness of the photocatalyst layer was measured by observation with a scanning electron microscope, it was about 0.5 μm in any of Examples 17-23. Thus, an intermediate layer and a photocatalyst layer were formed to obtain a photocatalyst-coated body.
こうして得られた５０×１００ｍｍの大きさの光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体をＪＩＳ Ｂ７７５３に規定されるサンシャインウエザオメーター（スガ試験機製 Ｓ−３００Ｃ）に投入した。３００ｈｒ経過後に試験片を取り出し、日本電色製の測色差計ＺＥ２０００にて、促進試験前後で色差を測定し、そのΔｂ値を比較することで変色の度合いを評価した。 About the photocatalyst coating body of a magnitude | size of 50x100 mm obtained in this way, the weather resistance test was done as follows. The photocatalyst-coated body was put into a sunshine weatherometer (S-300C, manufactured by Suga Test Instruments) defined in JIS B7753. After 300 hours, the test piece was taken out, the color difference was measured before and after the acceleration test with a color difference meter ZE2000 manufactured by Nippon Denshoku, and the degree of color change was evaluated by comparing the Δb values.
得られた結果は表７に示される通りであった。ここで、表中のＧはほとんど変色しなかったことを、ＮＧはΔｂ値がプラス側（黄変側）に推移したことを表す。表７に示されるように、光触媒層中の光触媒の含有量を２０質量部未満にすることによって、ケイ素原子含有量が小さい中間層に光触媒層を塗装しても充分な耐候性を有することが分かった。 The obtained results were as shown in Table 7. Here, G in the table indicates that the color has hardly changed, and NG indicates that the Δb value has shifted to the plus side (yellowing side). As shown in Table 7, by making the photocatalyst content in the photocatalyst layer less than 20 parts by mass, the photocatalyst layer has sufficient weather resistance even when the photocatalyst layer is applied to the intermediate layer having a small silicon atom content. I understood.
例２４、２５：塗膜の耐候性評価−２
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材として亜鉛メッキ鋼板に汎用のエポキシ樹脂系の下塗り剤を塗装し、乾燥したものを用意した。表１のＭ−１およびＭ−４に記載の中間層コーティング液をスプレーコートし、１２０℃で乾燥し中間層を得た。Ｍ−１およびＭ−４液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、例２４、２５のいずれの例においても約１０μｍであった。
Examples 24 and 25: Evaluation of weather resistance of coating film-2
The photocatalyst coating body provided with the intermediate | middle layer and the photocatalyst layer was manufactured as follows. First, a general-purpose epoxy resin-based primer was applied to a galvanized steel sheet as a base material and dried. The intermediate layer coating solutions described in M-1 and M-4 in Table 1 were spray coated and dried at 120 ° C. to obtain an intermediate layer. The solid content concentration of the resin in the M-1 and M-4 solutions was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm in both Examples 24 and 25.
一方、光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカと、溶媒として水とを表２のＴ−４に示される配合比で混合して、光触媒コーティング液を得た。光触媒コーティング液中の光触媒および無機酸化物の合計の固形分濃度は５．５質量％とした。得られた光触媒コーティング液をあらかじめ加熱した上記中間層塗装体上にスプレー塗布し、１２０℃で乾燥した。走査型電子顕微鏡観察により光触媒層の膜厚を測定したところ、例２４、２５のいずれの例においても約０．５μｍであった。こうして、中間層と光触媒層を形成させて、光触媒塗装体を得た。 On the other hand, a titania aqueous dispersion as a photocatalyst, a water-dispersed colloidal silica as an inorganic oxide, and water as a solvent were mixed at a mixing ratio shown by T-4 in Table 2 to obtain a photocatalyst coating solution. . The total solid concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating solution was 5.5% by mass. The obtained photocatalyst coating liquid was spray-coated on the intermediate layer-coated body heated in advance and dried at 120 ° C. When the film thickness of the photocatalyst layer was measured by observation with a scanning electron microscope, it was about 0.5 μm in both Examples 24 and 25. Thus, an intermediate layer and a photocatalyst layer were formed to obtain a photocatalyst-coated body.
こうして得られた５０×１００ｍｍの大きさの光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体をメタリングウエザメーター（スガ試験機製 Ｍ６Ｔ）に投入した。１５０ｈｒ経過後に試験片の外観を目視で確認した。 About the photocatalyst coating body of a magnitude | size of 50x100 mm obtained in this way, the weather resistance test was done as follows. The photocatalyst-coated body was put into a metering weather meter (M6T manufactured by Suga Test Instruments). The appearance of the test piece was visually confirmed after 150 hours had elapsed.
中間層に、シリコーン変性樹脂の固形分に対してケイ素原子含有量が１０質量％のアクリル変性シリコーン樹脂を用いた例２４は、クラックの発生が認められず、外観が良好で、十分な耐候性を有することがわかった。一方、ケイ素原子含有量が１６．５質量％のアクリル変性シリコーン樹脂を用いた例２５では、わずかではあるが、部分的にクラックの発生が認められた。 In Example 24, in which an acrylic modified silicone resin having a silicon atom content of 10% by mass with respect to the solid content of the silicone modified resin was used for the intermediate layer, no cracks were observed, the appearance was good, and sufficient weather resistance. It was found to have On the other hand, in Example 25 using an acrylic-modified silicone resin having a silicon atom content of 16.5% by mass, generation of cracks was partially observed.
例２６：塗膜の耐候性評価−３
基材のサイズを１５０×６５ｍｍとした以外は例２４と同じ条件で、光触媒塗装体を作成した。この光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体をＪＩＳ Ｂ７７５３に規定されるサンシャインウエザオメーター（スガ試験機製 Ｓ−３００Ｃ）に投入した。４５００ｈｒ経過後に試験片を取り出し、日本電色製の測色差計ＺＥ２０００にて色差を測定し、ΔＥ値を算出した。また接触角計（協和界面科学製 ＣＡ−Ｘ１５０）にて水接触角を測定した。なおΔＥ値は、ＪＩＳ Ｚ８７３０に記載の方法に基づいて算出した。
Example 26: Evaluation of weather resistance of coating film-3
A photocatalyst-coated body was prepared under the same conditions as in Example 24 except that the size of the substrate was 150 × 65 mm. About this photocatalyst coating body, the weather resistance test was done as follows. The photocatalyst-coated body was put into a sunshine weatherometer (S-300C manufactured by Suga Test Instruments Co., Ltd.) defined in JIS B7753. After 4500 hours had elapsed, the test piece was taken out, the color difference was measured with a color difference meter ZE2000 manufactured by Nippon Denshoku, and the ΔE value was calculated. Moreover, the water contact angle was measured with the contact angle meter (Kyowa Interface Science CA-X150). The ΔE value was calculated based on the method described in JIS Z8730.
本発明において得られた光触媒塗装体は、サンシャインウエザオメーター４５００ｈｒ経過後のΔＥ値が０．５、水接触角は５°以下と驚異的な耐候性と、超親水性を有することが分かった。またＮＯｘガス分解および塗膜の密着性も、初期とほとんど同等のレベルであった。 The photocatalyst-coated body obtained in the present invention was found to have surprising weather resistance and super hydrophilicity, with a ΔE value of 0.5 and a water contact angle of 5 ° or less after 4500 hours of sunshine weatherometer. . Moreover, the NOx gas decomposition and the adhesion of the coating film were almost the same level as in the initial stage.
例２７：塗膜の耐候性評価−４
例２６と同一条件にて作成した光触媒塗装体について、以下の通り耐候性試験を行った。光触媒塗装体を神奈川県茅ケ崎市にて、水平から上方に向け４５°の傾斜をつけた状態で南の方角に向け、屋外曝露を実施した。約５００日経過後に試験片を取り出し、日本電色製の測色差計ＺＥ２０００にて色差を測定した。
Example 27: Evaluation of weather resistance of coating film-4
About the photocatalyst coating body produced on the same conditions as Example 26, the weather resistance test was done as follows. The photocatalyst-coated body was exposed outdoors in Chigasaki City, Kanagawa Prefecture, with a 45 ° slope from the horizontal to the top, facing south. After about 500 days, the test piece was taken out and the color difference was measured with a color difference meter ZE2000 manufactured by Nippon Denshoku.
本発明において得られた光触媒塗装体は、屋外曝露を実施した約５００日経過後のΔＥ値が０．５以下と、驚異的な防汚性を有することが分かった。 The photocatalyst-coated body obtained in the present invention was found to have an amazing antifouling property, with a ΔE value of about 0.5 or less after about 500 days after outdoor exposure.
例２８、２９：耐光性評価
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロート板ガラスを用意した。あらかじめ加熱したガラス基材上に、表１のＭ−２およびＭ−５に記載の中間層コーティング液をスプレーコートし、１２０℃で乾燥し中間層を得た。このＭ−２およびＭ−５液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、例２８、２９のいずれの例においても約１０μｍであった。
Examples 28 and 29: Light resistance evaluation A photocatalyst-coated body provided with an intermediate layer and a photocatalyst layer was produced as follows. First, a float plate glass was prepared as a base material. On the glass substrate heated beforehand, the intermediate | middle layer coating liquid as described in M-2 of Table 1 and M-5 was spray-coated, and it dried at 120 degreeC, and obtained the intermediate | middle layer. The solid content concentration of the resin in the M-2 and M-5 solutions was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm in both examples 28 and 29.
こうして得られた５０×５０ｍｍの大きさの中間層塗装体について、３００〜４００ｎｍの紫外線の透過率の測定を紫外・可視・近赤外分光光度計（島津製作所製 ＵＶ−３１５０）を用いて行った。 The intermediate layer coated body having a size of 50 × 50 mm thus obtained was measured for ultraviolet transmittance of 300 to 400 nm using an ultraviolet / visible / near infrared spectrophotometer (UV-3150, manufactured by Shimadzu Corporation). It was.
得られた結果は図１に示される通りであった。紫外線吸収剤を添加した例２８において、３００〜４００ｎｍの紫外線透過率は１０％以下となり、紫外線を十分に遮蔽することが確認できた。 The obtained result was as shown in FIG. In Example 28 in which the ultraviolet absorber was added, the ultraviolet transmittance at 300 to 400 nm was 10% or less, and it was confirmed that the ultraviolet rays were sufficiently shielded.
例３０：ガス分解性の評価−２
中間層および光触媒層を備えた光触媒塗装体を以下の通り製造した。まず、基材としてフロート板ガラスを用意した。あらかじめ加熱したガラス基材上に、表１のＭ−１に記載の中間層コーティング液をスプレーコートし、１２０℃で乾燥し中間層を得た。このＭ−１液中の樹脂の固形分濃度は約２０質量％であった。走査型電子顕微鏡観察により中間層の膜厚を測定したところ、約１０μｍであった。
Example 30: Evaluation of gas decomposability-2
The photocatalyst coating body provided with the intermediate | middle layer and the photocatalyst layer was manufactured as follows. First, a float plate glass was prepared as a base material. On the glass substrate heated beforehand, the intermediate | middle layer coating liquid as described in M-1 of Table 1 was spray-coated, and it dried at 120 degreeC, and obtained the intermediate | middle layer. The solid content concentration of the resin in this M-1 solution was about 20% by mass. When the film thickness of the intermediate layer was measured by observation with a scanning electron microscope, it was about 10 μm.
一方、光触媒としてのチタニア水分散体と、無機酸化物としての水分散型コロイダルシリカとを、表２のＴ−４に示される配合比で水および１−プロパノールと混合して、加水分解性シリコーンを含有しない光触媒コーティング液を得た。光触媒コーティング液中の、光触媒および無機酸化物の合計の固形分濃度は５．５質量％とした。なお、この光触媒コーティング液は界面活性剤を添加する代わりに１−プロパノールを光触媒コーティング液に対して２０質量％となるように配合した。得られた光触媒コーティング液をあらかじめ加熱した上記中間層塗装体上にスプレー塗布し、１２０℃で乾燥した。走査型電子顕微鏡観察により光触媒層の膜厚を測定したところ、約０．５μｍであった。こうして、中間層と光触媒層を形成させて、光触媒塗装体を得た。 On the other hand, a titania aqueous dispersion as a photocatalyst and a water-dispersed colloidal silica as an inorganic oxide are mixed with water and 1-propanol at a blending ratio shown by T-4 in Table 2 to produce a hydrolyzable silicone. A photocatalyst coating solution containing no benzene was obtained. The total solid content concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating liquid was 5.5% by mass. In addition, this photocatalyst coating liquid was mix | blended so that it might become 20 mass% with respect to a photocatalyst coating liquid instead of adding surfactant. The obtained photocatalyst coating liquid was spray-coated on the intermediate layer-coated body heated in advance and dried at 120 ° C. When the film thickness of the photocatalyst layer was measured by observation with a scanning electron microscope, it was about 0.5 μm. Thus, an intermediate layer and a photocatalyst layer were formed to obtain a photocatalyst-coated body.
こうして得られた５０×１００ｍｍの大きさの光触媒塗装体について、例４と同様の方法でガス分解性試験を行ったところ、例４と同等の結果となった。
The photocatalyst-coated body having a size of 50 × 100 mm thus obtained was subjected to a gas decomposability test in the same manner as in Example 4. As a result, the same result as in Example 4 was obtained.
Claims (13)
前記中間層は有機防カビ剤および紫外線吸収剤を含んでなり、
前記光触媒層が、
１質量部以上２０質量部未満の光触媒粒子と、
７０質量部を超え９９質量部以下の無機酸化物粒子と、
０質量部以上１０質量部未満の加水分解性シリコーンとを、
前記光触媒粒子、前記無機酸化物粒子、および前記加水分解性シリコーンの合計量が１００質量部となるように含んでなる光触媒塗装体。 A photocatalyst-coated body comprising a base material, an intermediate layer provided on the base material, and a photocatalyst layer provided on the intermediate layer,
The intermediate layer comprises an organic antifungal agent and an ultraviolet absorber,
The photocatalytic layer is
1 to 20 parts by mass of photocatalyst particles,
Inorganic oxide particles exceeding 70 parts by mass and 99 parts by mass or less;
0 part by mass or more and less than 10 parts by mass hydrolyzable silicone,
A photocatalyst-coated body comprising a total amount of the photocatalyst particles, the inorganic oxide particles, and the hydrolyzable silicone of 100 parts by mass.
１質量部以上２０質量部未満の光触媒粒子と、
７０質量部を超え９９質量部以下の無機酸化物粒子と
０質量部以上１０質量部未満の加水分解性シリコーンとを、
前記光触媒粒子、前記無機酸化物粒子、および前記加水分解性シリコーンの合計量が１００質量部となるように含んでなる溶質が分散されてなる、光触媒コーティング液。 It is a photocatalyst coating liquid used for manufacture of the photocatalyst coating body as described in any one of Claims 1-6, Comprising: In a solvent,
1 to 20 parts by mass of photocatalyst particles,
More than 70 parts by weight and 99 parts by weight or less of inorganic oxide particles and 0 parts by weight or more and less than 10 parts by weight of hydrolyzable silicone,
A photocatalyst coating liquid in which a solute containing the photocatalyst particles, the inorganic oxide particles, and the hydrolyzable silicone is dispersed so that the total amount becomes 100 parts by mass.
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